JPH0675126B2 - Crystal fiber manufacturing method - Google Patents
Crystal fiber manufacturing methodInfo
- Publication number
- JPH0675126B2 JPH0675126B2 JP61202889A JP20288986A JPH0675126B2 JP H0675126 B2 JPH0675126 B2 JP H0675126B2 JP 61202889 A JP61202889 A JP 61202889A JP 20288986 A JP20288986 A JP 20288986A JP H0675126 B2 JPH0675126 B2 JP H0675126B2
- Authority
- JP
- Japan
- Prior art keywords
- base material
- crystal
- fiber
- powder
- crystal fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/16—Heating of the molten zone
- C30B13/22—Heating of the molten zone by irradiation or electric discharge
- C30B13/24—Heating of the molten zone by irradiation or electric discharge using electromagnetic waves
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、Al2O3、YAG、LiNbO3などの結晶からなり、
固体レーザ用媒質、フアイバ形アイソレータ、耐熱性フ
アイバなどとして使用される結晶フアイバを製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention comprises crystals of Al 2 O 3 , YAG, LiNbO 3, etc.,
The present invention relates to a method for producing a crystal fiber used as a medium for a solid-state laser, a fiber isolator, a heat resistant fiber, or the like.
従来、このような結晶フアイバは、単結晶の溶融、引上
げ法によつて製造されている。すなわち、溶融ルツボ内
に上記結晶を溶融状態で満たし、種結晶を収容したシエ
イバを融液に接触させ、徐々に種結晶を引き上げること
により、単結晶からなる長尺の結晶フアイバを得るもの
である。Conventionally, such a crystal fiber is manufactured by a method of melting and pulling a single crystal. That is, the crystal is filled in a molten crucible in a molten state, the seed crystal-containing shear is brought into contact with the melt, and the seed crystal is gradually pulled up to obtain a long crystal fiber made of a single crystal. .
しかしながら、このような製法では、原料となる酸化物
等を高純度に精製する必要があるが、原料となる酸化物
等は、高融点であるためその精製が困難であり、かつ純
度も十分なものが得られにくいという問題がある。However, in such a production method, it is necessary to purify the starting material oxide or the like to a high purity, but the starting material oxide or the like has a high melting point, so that the purification is difficult and the purity is sufficient. There is a problem that it is difficult to obtain things.
また、CrドープAl2O3などの２成分からなる結晶フアイ
バを得る場合には、CrO3粉末とAl2O3粉末とを混合し、
これを溶融して引上げる方法が採用されるが、粉末状態
および溶融状態においてもCrO3の分散がミクロ的に均一
に行われず、得られる結晶フアイバ中でのCr原子の分布
が不均一になると云う問題もある。Further, when a crystalline fiber composed of two components such as Cr-doped Al 2 O 3 is obtained, CrO 3 powder and Al 2 O 3 powder are mixed,
Although a method of melting and pulling this up is adopted, if the distribution of CrO 3 is not performed microscopically even in the powder state and the molten state, and the distribution of Cr atoms in the obtained crystal fiber becomes uneven. There is also a problem.
さらに、溶融ルツボを用いるため、これによる汚染もあ
り、多成分系の溶融物から低融点成分が溶融途中におい
て揮発すると云う問題もある。Further, since a molten crucible is used, there is also contamination due to this, and there is also a problem that the low melting point component volatilizes during melting from the multi-component melt.
そこで、この発明においては、有機金属化合物のゲルを
生成せしめ、このゲルを乾燥して粉末とし、この粉末を
加熱加圧して柱状の母材を得、この母材の端部をレーザ
ー加熱して溶融引上げして結晶フアイバを得ることによ
つて、上記諸問題を解決した。Therefore, in the present invention, a gel of an organometallic compound is generated, the gel is dried to form a powder, the powder is heated and pressed to obtain a columnar base material, and the end portion of the base material is laser-heated. The above problems were solved by obtaining a crystalline fiber by melting and pulling up.
この発明では出発原料として有機金属化合物を使用す
る。この有機金属化合物としては、結晶フアイバをなす
Cr,Al,Feなどの金属元素とエトキシ基、メトキシ基など
の加水分解可能な有機基との化合物が用いられる。そし
て、結晶フアイバをなす結晶の種類に応じて有機金属化
合物の種類、その組合せおよび量比が決められる。例え
ば、結晶にAl2O3を用いるときは、有機金属化合物とし
てAl(Oi-Pr)3を用い、結晶にCrドープAl2O3を用いると
きは、有機金属線化合物としてAl(Oi-Pr)3と少量のCr(A
c)3とが用いられる。以下、結晶組成とそれを得るため
の有機金属化合物の組合せ例を例示する。In this invention, an organometallic compound is used as a starting material. This organometallic compound forms a crystalline fiber.
A compound of a metal element such as Cr, Al or Fe and a hydrolyzable organic group such as an ethoxy group or a methoxy group is used. Then, the kind of the organometallic compound, the combination and the amount ratio thereof are determined according to the kind of the crystal forming the crystal fiber. For example, when Al 2 O 3 is used for the crystal, Al (Oi-Pr) 3 is used as the organometallic compound, and when Cr-doped Al 2 O 3 is used for the crystal, Al (Oi-Pr) is used as the organometallic compound. ) 3 and a small amount of Cr (A
c) 3 and are used. Hereinafter, a combination example of the crystal composition and the organometallic compound for obtaining the crystal composition will be exemplified.
結晶組成 有機金属化合物の組立合せ YAG Y(Oi-Pr)3、Al(Oi-Pr)3 YIG Y(Oi-Pr)3、Fe(OEt)3 GGG Ga(OEt)3、Gd(Oi-Pr)2 LiNbO3 Li(OEt)、Nb(OEt)5 LiTaO3 Li(OEt)、Ta(OEt)5 Li2B4O7 Li(OEt)、B(OEt)3 但し、有機金属化合物中の（Oi−Pr）はイソプロピルオ
キシド基を、（Ac）はアセテル基を、（OEt）はエトキ
シ基を示す。Crystal composition Organometallic compound assembly YAG Y (Oi-Pr) 3 , Al (Oi-Pr) 3 YIG Y (Oi-Pr) 3 , Fe (OEt) 3 GGG Ga (OEt) 3 , Gd (Oi-Pr ) 2 LiNbO 3 Li (OEt), Nb (OEt) 5 LiTaO 3 Li (OEt), Ta (OEt) 5 Li 2 B 4 O 7 Li (OEt), B (OEt) 3 However, in the organometallic compound, (Oi-Pr) represents an isopropyl oxide group, (Ac) represents an acetyl group, and (OEt) represents an ethoxy group.
これらの有機金属化合物は、イオン交換、クロマトグラ
フ、精密蒸溜などの高純化手段により、少なくとも99.9
9％以上の純度を有するものが用いられる。These organometallic compounds are at least 99.9% by high purification means such as ion exchange, chromatography, precision distillation.
Those having a purity of 9% or more are used.
ついで、これらの有機金属化合物は、その１種以上がそ
れぞれ混合モル比が決められたうえ、水あるいはメタノ
ール、エタノールなどのアルコール類に溶解され、溶液
とされる。この溶液中の上記有機金属化合物の濃度は通
常10〜30wt％程度とされる。ついで、この溶液に必要に
応じて塩酸やアンモニアを加えて、30〜80℃で0.5〜50
時間加熱攪拌し、有機金属化合物を加水分解し、ゲル化
する。Next, one or more of these organometallic compounds, each having a mixing molar ratio determined, are dissolved in water or an alcohol such as methanol or ethanol to form a solution. The concentration of the organometallic compound in this solution is usually about 10 to 30 wt%. Then, add hydrochloric acid or ammonia to this solution as needed, and add 0.5 to 50 at 30 to 80 ° C.
The mixture is heated and stirred for a period of time to hydrolyze the organometallic compound and gelate.
ゲル化が終了したら、このゲルを80〜150℃程度に加熱
し、水あるいはアルコールを除去し、さらに500〜900℃
で２〜10時間加熱してゲルを粉末化する。この粉末化の
時点において、有機金属化合物は金属酸化物、金属酸素
酸塩等になり、結晶組成と同一の組成となる。なお、塩
酸、アンモニアは上記加熱時に揮散し、粉末中には全く
残らない。When gelation is complete, heat this gel to about 80-150 ° C to remove water or alcohol, then 500-900 ° C.
Heat for 2-10 hours to pulverize the gel. At the time of this pulverization, the organometallic compound becomes a metal oxide, a metal oxyacid salt, or the like, and has the same composition as the crystal composition. Hydrochloric acid and ammonia volatilize during the above heating and do not remain in the powder at all.
ついで、この粉末を円筒状の容器等に収容して加熱加圧
し、柱状の母材とする。この加熱加圧は温度1000〜2000
℃、圧力1000〜3000kg/cm2として、通常の油圧プレス、
静水圧プレスなどを用いて行われる。この加熱加圧は、
粉末の融点未満の温度で行われるが、高圧力が加わるこ
とにより、粉末粒子同士が密着固結し、固い柱状体とな
る。Next, this powder is housed in a cylindrical container or the like and heated and pressed to form a columnar base material. This heating and pressurization is temperature 1000-2000
C, pressure 1000 ~ 3000kg / cm 2 , normal hydraulic press,
It is performed using a hydrostatic press or the like. This heating and pressing is
Although it is performed at a temperature lower than the melting point of the powder, high pressure is applied to the powder particles so that they adhere to each other and solidify to form a solid columnar body.
次に、得られた柱状母材の一端をレーザ加熱により加熱
溶融し、溶融引き上げによつて結晶フアイバを得る。こ
のレーザ加熱による溶融引き上げは、例えば第１図に示
すような装置によつて行われる。第１図において、CO2
レーザ装置などのレーザ源１から発射されたレーザ光
は、レンズ２を通り反射鏡３で二分される。二分された
レーザ光はそれぞれ反射鏡4,4′、5,5′で反射されて方
向が変えられ、凹面鏡6,6′で集光されて母材７の先端
に照射されるようになつている。母材７はレーザ光の照
射によりその先端部が溶融する。この溶融部分に種単結
晶を接触させて徐々に引き上げれば、単結晶からなる結
晶フアイバ８がえられる。この溶融引上げの際、その雰
囲気を酸素雰囲気とし、酸化物や酸素酸塩からなる結晶
の酸化状態を安定に保持することが好ましい。Next, one end of the obtained columnar base material is heated and melted by laser heating, and a crystal fiber is obtained by melting and pulling. The melting and pulling by the laser heating is performed by an apparatus as shown in FIG. 1, for example. In Fig. 1, CO 2
Laser light emitted from a laser source 1 such as a laser device passes through a lens 2 and is divided into two by a reflecting mirror 3. The bisected laser light is reflected by the reflecting mirrors 4, 4 ', 5, 5'and the directions thereof are changed, and is condensed by the concave mirrors 6, 6'and applied to the tip of the base material 7. There is. The tip of the base material 7 is melted by the irradiation of laser light. When the seed single crystal is brought into contact with this melted portion and gradually pulled up, the crystal fiber 8 made of the single crystal is obtained. At the time of this melting and pulling up, it is preferable that the atmosphere is an oxygen atmosphere and the oxidation state of crystals made of oxides or oxyacid salts is stably maintained.
このような結晶フアイバの製法によれば、出発原料とし
て常温で液体の有機金属化合物を用いているので、精密
蒸溜、イオン交換などの通常の高純化方法により容易か
つ十分に高純化されたものを使用することができる。ま
た、有機金属化合物を２種以上混合する場合は、液状で
混合できるので、分子レベルでの混合が可能であり、極
めて均一な混合が可能となり、組成の均一なフアイバが
得られる。また、加熱、加圧によつて母材を作成し、こ
の母材からフアイバ化を行うようにしているので、レー
ザ光を利用した溶融紡糸が行え、溶融ルツボを使う必要
がなく、ルツボによる汚染がなく、母材の溶融部分が微
少領域で溶融時間も短時間で済むことから低融点成分の
揮散がない。さらに、母材を加熱加圧して固結している
ので、溶融紡糸時に母材が変形したり、クラックが生じ
たりする不都合もない。According to such a method for producing a crystalline fiber, since an organometallic compound that is liquid at room temperature is used as a starting material, it is possible to use an easily and sufficiently highly purified substance that has been easily purified by a conventional high purification method such as precision distillation and ion exchange. Can be used. In addition, when two or more kinds of organometallic compounds are mixed, they can be mixed in a liquid state, so that they can be mixed at a molecular level, extremely uniform mixing is possible, and a fiber having a uniform composition can be obtained. In addition, since the base material is created by heating and pressurizing and the fiber is made from this base material, melt spinning using laser light can be performed, and there is no need to use a melting crucible, and contamination by the crucible is possible. In addition, since the molten portion of the base material is in a minute region and the melting time is short, the low melting point component does not evaporate. Further, since the base material is heated and pressed to be solidified, there is no inconvenience that the base material is deformed or cracked during melt spinning.
以下、実施例を示して具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
（実施例１） Al(OEt)3300gとCr(Ac)31gとを、1000mlの水、500mlのエ
タノール、100mlのアンモニア水（17wt％）の混合液に
溶解した。この溶液を80℃で30時間攪拌し、ゲル化させ
た。このゲルを120℃で40時間加熱して、水分、アルコ
ール分を除去し、さらに500℃で２時間加熱して白色粉
末を得る。Example 1 300 g of Al (OEt) 3 and 1 g of Cr (Ac) 3 were dissolved in a mixed solution of 1000 ml of water, 500 ml of ethanol and 100 ml of ammonia water (17 wt%). This solution was stirred at 80 ° C. for 30 hours to cause gelation. This gel is heated at 120 ° C for 40 hours to remove water and alcohol, and further heated at 500 ° C for 2 hours to obtain a white powder.
この粉末を600℃、2000kg/cm2の条件で加熱加圧し、径
2.0mm、長さ100mmの母材とした。ついで、出力15WのCO2
レーザをレーザ源としたレーザ溶融紡糸装置を使用し
て、母材の一端から溶融紡糸し、径200μｍのCrドープA
l2O3結晶フアイバを得た。This powder was heated and pressed under the conditions of 600 ° C and 2000 kg / cm 2 ,
The base material has a length of 2.0 mm and a length of 100 mm. Then, output 15W CO 2
Using a laser melt spinning device with a laser as the laser source, melt spinning from one end of the base material and Cr-doped A with a diameter of 200 μm
An l 2 O 3 crystal fiber was obtained.
得られたフアイバは、従来法によつて得られたものに比
べてドーバントのCr原子の分布が均一であり、また不純
物も微かで良好な特性を示した。The fiber obtained had a more uniform distribution of Cr atoms in the dovant than the one obtained by the conventional method, and had a slight impurity and showed good characteristics.
〔実施例２〕 Li（OEt）200mlとNd(OEt)5200mlとを水1000ml、メタノ
ール500mlの混合液に溶解し、80℃で20時間攪拌、混合
し、ゲル化する。ついで、このゲルを120℃で40時間加
熱して、水、メタノールを除去し、さらに500℃で１時
間加熱して粉末とする。Example 2 200 ml of Li (OEt) and 200 ml of Nd (OEt) 5 are dissolved in a mixed solution of 1000 ml of water and 500 ml of methanol, and the mixture is stirred and mixed at 80 ° C. for 20 hours to gel. Then, this gel is heated at 120 ° C. for 40 hours to remove water and methanol, and further heated at 500 ° C. for 1 hour to obtain a powder.
この粉末を800℃、2000kg/cm2の条件で加熱加圧し、径
2.0mm、長さ100mmの母材を得た。この母材から実施例１
と同様にして径100μｍのLiNbO3単結晶フアイバを得
た。This powder was heated and pressed under the conditions of 800 ° C and 2000 kg / cm 2 ,
A base material having a length of 2.0 mm and a length of 100 mm was obtained. Example 1 from this base material
A LiNbO 3 single crystal fiber having a diameter of 100 μm was obtained in the same manner as in.
このフアイバは不純物が微かであり、良好な電気光学効
果を有していた。This fiber had minute impurities and had a good electro-optical effect.
〔発明の効果〕 以上説明したように、この発明の結晶フアイバの製法
は、出発原料として高純度品が容易に入手できる有機金
属化合物を用い、これのゲルを作成し、このゲルを乾燥
して粉末とし、この粉末を加熱加圧して柱状の母材と
し、この母材からレーザ加熱によつて結晶フアイバを溶
融紡糸するものであるので、出発原料に由来する不純物
や製造途中で混入する不純物が微少であり、また結晶の
組成が均一となり、良好な特性を有する結晶フアイバを
得ることができる。[Effects of the Invention] As described above, the production method of the crystalline fiber of the present invention uses an organometallic compound as a starting raw material, which is easily available as a high-purity product, prepares a gel thereof, and then the gel is dried. As a powder, the powder is heated and pressed to form a columnar base material, and the crystal fiber is melt-spun by laser heating from the base material. A crystal fiber having a small amount and a uniform crystal composition can be obtained, and a crystal fiber having good characteristics can be obtained.
第１図はこの発明の製法において用いられるレーザ溶融
紡糸装置の例を示す概略構成図である。 ７……母材 ８……結晶フアイバ。FIG. 1 is a schematic configuration diagram showing an example of a laser melt spinning apparatus used in the production method of the present invention. 7: Base material 8: Crystal fiber.
Claims (1)
作成し、このゲルを乾燥して粉末とし、この粉末を加熱
加圧して柱状の母材とし、この母材の端部をレーザー加
熱して溶融し、結晶フアイバを得ることを特徴とする結
晶フアイバの製法。1. A gel comprising at least one organometallic compound is prepared, the gel is dried into a powder, the powder is heated and pressed into a columnar base material, and the end portion of the base material is laser-heated. A method for producing a crystal fiber, which comprises melting and melting to obtain a crystal fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61202889A JPH0675126B2 (en) | 1986-08-29 | 1986-08-29 | Crystal fiber manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61202889A JPH0675126B2 (en) | 1986-08-29 | 1986-08-29 | Crystal fiber manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6358404A JPS6358404A (en) | 1988-03-14 |
| JPH0675126B2 true JPH0675126B2 (en) | 1994-09-21 |
Family
ID=16464879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61202889A Expired - Fee Related JPH0675126B2 (en) | 1986-08-29 | 1986-08-29 | Crystal fiber manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0675126B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4565233B2 (en) * | 2003-02-20 | 2010-10-20 | 株式会社キャンパスクリエイト | Flow rate measuring method and measuring apparatus used therefor |
| JP2021160977A (en) * | 2020-03-31 | 2021-10-11 | 株式会社クリスタルシステム | Infrared irradiation device |
-
1986
- 1986-08-29 JP JP61202889A patent/JPH0675126B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6358404A (en) | 1988-03-14 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |